Cyano-ethanolpyridines



CYANO-ETHANOLPYRIDINES Francis E. Cislak, Indianapolis, Ind., assignor to Reilly Tar 8: Chemical Corporation, Indianapolis, Ind., a corporation of Indiana No Drawing. Filed July '20, 1959, Ser. No. 828,033

7 Claims. (01. 266-2949 This invention relates to new chemical compounds and Some of my cyano-ethanolpyridines may also be prepared by reacting a quaternary salt of the N-oxide of an ethanolpyridine with KCN. The equation below portrays the formation of 2-cyano-3-ethanolpyridine from 3-ethanolpyridine-N-oxide:

C-CHa KCN H RR I O The above process of making cyano ethanolpyridines, as

to the process of making them. More particularly, it

relates to cyano-ethanolpyridines'having the following structural formulae:

CHiCHzOH tion of cyano-vinylpyridines which latter compounds are described and claimed in my co-pending application Serial Number 781,830, filed December 22, 1958. My cyanoethanolpyridines may be used in the preparation of aminomethylethanolpyridines:

NC [El H2N.CH

CHCHQOH CHzCHgOH And they may be hydrolysed, as with dilute caustic soda, to give ethanolpyridine carboxylic acids or amides:

The ethanolpyridine carboxylic acids are useful in the preparation of vinylpyridine carboxylic acids.

. Oxidation, with nitric acid, con erts my cyano-ethanolpyridines to cyanopyridine carboxylic acids:

NC NC HNO: 0

" tion with the following specific examples.

well as other,cyano-alkanolpyridines, is thezsubiectifof my copending application Serial No. 845,634,.fi1ed October 12, 1959.

My invention will be described more fully in conjunc- It should be understood, however, that these examples are given by way of illustration only, and that my invention is not to be limited by the details set forth therein.

EXAMPLE 1 5 -cyan0-2-ethan0lpyridine A mixture of 1,200 grams of 2-methyl-5-cyanopyridine and 35 grams of para-formaldehyde is placed into a stainless steel pressure vessel provided with means for' 5 heating and agitating. The vessel is closed, heated to about 70 C.; the agitation is now started. While continuing the agitation, the temperature of the vessel is raised to about 140? C. at which temperature it is held for from about 15' minutes to about one hour. Then the vessel is cooled to about 30 C., and the contents poured into a distillation'flaslr. The excess Z-methyl-S- cyanopyridine is removed by distillation under vacuum. The residue remaining after the Z-methyl-S-cyanopyridine is distilled oli is a semi-refined S-cyanO-Z-ethanoIpyridine.

My cyanaethanolpyfidines are useful in the prepam It is useful as 1s for the preparation of 2-v1nyl-5-cyanopyridine. If a purer S-cyano-Z-ethanolpyridine is desired, the residue is subjected to high vacuum distillation. The distillate is about -98% pure 5-cyano-2-ethanolpyridine. It boils above about C. at 15 mm. Hg pressure.

EXAMPLE 2 4-cyan0-2-ethan0lpyridine CHrCHzOH The procedure of Example 1 is repeated except that 2-methyl-4-cyanopyridine is used in place of the 2-methyl- S-cyanopyridine.

EXAMPLE 3 2-ethanol-4-cyanopyridine and 2-ethanol-6-cyan0pyridine NC OHzOHrOH To an aqueous solution of 282 grams of the methyl Filmed M 2 1 9a iodide quaternary salt at 3 2-ethan-Z-olpyridine-N-dxide there is added 70 grams of KCN. The mixture is stirred, at room temperature, for about four hours. The solution is thenezrtracted with chloroform, and the 2-.ethanola4- cyanopyridine and the 2-ethanol-6 cyanopyridine are recovered from the chloroform extract by fractional distillation under high vacuum. The 2-ethanol-6-cyanopyridine isomer predominates.

EXAMPLE 4 2-ethanol-3-cyanopyridine CHQCHQOH Th procedure of Example 1 is repeated with the exception that '2-methyl3cyanopyridine is used in place of the Z-methyl-S-cyanopyridine.

. EXAMPLE 5 4 .ethanal-Leyanopyridine time E2011 7. ON N and a where R is selected from the group consisting of hydro- The procedure of Example 1 is repeated with the exception that 2-cyano-4-methylpyridiue is used in place of the 2-methyl-5-cyanopyridin'e.

I claim as my invention:

1. A compound of the class consisting of 2-ethanolcyanopyridines and 4-ethanol-cyanopyridines having the structural formulae:

and

gen and lower alkyl which comprises preparing a mixture of formaldehyde with a compound of the class consisting of Z-methyl-cyanopyridin and 4-methyl-cyanopyridine which compounds have the structural formulae:

and

where R is selected from the group consisting of hydrogen and lower alkyl, heating the resultant mixture to a temperature of about for from about 15 minutes to about one hour, and recovering the resultant cyanoethanolpyridine.

No references cited. 

1. A COMPOUND OF THE CLASS CONSISTING OF 2-ETHANOLCYANOPYRIDINES AND 4-ETHONAL-CYANOPYRIDINES HAVING THE STRUCTURAL FORMULAE: 